U.S. patent application number 09/977146 was filed with the patent office on 2002-12-26 for synergistically active herbicidal mixtures.
Invention is credited to Haden, Egon, Hamprecht, Gerhard, Kibler, Elmar, Landes, Max, Mayer, Horst, Mulder, Christiaan, Nuyken, Wessel, Schonhammer, Alfons, Sievernich, Bernd, Walter, Helmut, Westphalen, Karl-Otto.
Application Number | 20020198106 09/977146 |
Document ID | / |
Family ID | 7772673 |
Filed Date | 2002-12-26 |
United States Patent
Application |
20020198106 |
Kind Code |
A1 |
Landes, Max ; et
al. |
December 26, 2002 |
Synergistically active herbicidal mixtures
Abstract
A composition which comprises a) at least one sulfonylurea of
the formula I 1 wherein the radicals R.sup.1 to R.sup.5 and the
index n are as defined in the specification, or an environmentally
compatible salt of the sulfonylurea, and b) at least one herbicidal
compound selected from groups b.sub.1 to b.sub.41 as defined in the
specification, or an environmentally compatible salt of the
herbicidal compound, and which exhibits a synergistic herbicidal
effect.
Inventors: |
Landes, Max; (Gonnheim,
DE) ; Sievernich, Bernd; (Bohl-Iggelheim, DE)
; Kibler, Elmar; (Hassloch, DE) ; Nuyken,
Wessel; (Otterstadt, DE) ; Walter, Helmut;
(Obrigheim, DE) ; Westphalen, Karl-Otto; (Speyer,
DE) ; Mayer, Horst; (Ludwigshafen, DE) ;
Haden, Egon; (Harthausen, DE) ; Mulder,
Christiaan; (Nelspruit, ZA) ; Schonhammer,
Alfons; (Mertesheim, DE) ; Hamprecht, Gerhard;
(Weinheim, DE) |
Correspondence
Address: |
KEIL & WEINKAUF
1350 CONNECTICUT AVENUE, N.W.
WASHINGTON
DC
20036
US
|
Family ID: |
7772673 |
Appl. No.: |
09/977146 |
Filed: |
October 15, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09977146 |
Oct 15, 2001 |
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09520224 |
Mar 7, 2000 |
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6362133 |
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09520224 |
Mar 7, 2000 |
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09043314 |
Feb 17, 1998 |
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6054410 |
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09043314 |
Feb 17, 1998 |
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PCT/EP96/03996 |
Sep 12, 1996 |
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Current U.S.
Class: |
504/189 |
Current CPC
Class: |
A01N 47/36 20130101;
A01N 47/36 20130101; A01N 61/00 20130101; A01N 47/36 20130101; A01N
37/40 20130101; A01N 47/36 20130101; A01N 37/40 20130101; A01N
47/36 20130101; A01N 2300/00 20130101 |
Class at
Publication: |
504/189 |
International
Class: |
A01N 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 20, 1995 |
DE |
19534910.5 |
Claims
We claim:
1. A herbicidal mixture comprising a) at least one derivative of a
sulfonylurea of the formula I 4 where the substituents have the
following meanings: R.sup.1 is C.sub.1-C.sub.6-alkyl which has
attached to it one to five of the following groups: methoxy,
ethoxy, SO.sub.2CH.sub.3, cyano, chlorine, fluorine, SCH.sub.3,
S(O)CH.sub.3; halogen; a group ER.sup.6 where E is O, S or
NR.sup.7; COOR.sup.8; NO.sub.2; S(O).sub.oR.sup.9,
SO.sub.2NR.sup.10R.sup.11, CONR.sup.10R.sup.11; R.sup.2 is
hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl, halogen, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-haloalkoxy; C.sub.1-C.sub.4-haloalkyl, a
C.sub.1-C.sub.2-alkylsulfonyl group, nitro, cyano or
C.sub.1-C.sub.4-alkylthio; R.sup.3 is F, CF.sub.3, CF.sub.2Cl,
CF.sub.2H, OCF.sub.3, OCF.sub.2Cl, or, if R.sup.1 is
CO.sub.2CH.sub.3 and R.sup.2 is simultaneosly fluorine, R.sup.3 is
Cl, or, if R.sup.1 is CH.sub.2CF.sub.3 or CF.sub.2CF.sub.3, R.sup.3
is methyl, or, if R.sup.4 is OCF.sub.3 or OCF.sub.2Cl, R.sup.3 is
OCF.sub.2H or OCF.sub.2Br; R.sup.4 is C.sub.1-C.sub.2-alkoxy,
C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkylthio,
C.sub.1-C.sub.2-alkylamino, di-C.sub.1-C.sub.2-alkylamino, halogen,
C.sub.1-C.sub.2-haloalkyl, C.sub.1-C.sub.2-haloalkoxy, R.sup.5 is
hydrogen, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.4-alkyl; R.sup.6 is
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl or C.sub.3-C.sub.6-cycloalkyl, all of which
can have attached to them 1 to 5 halogen atoms, with the exception
of allyl, difluoromethoxy, chlorodifluoromethoxy and
2-chloroethoxy, if E is O or S. In the event that E is O or
NR.sup.7, R.sup.6 is furthermore also methylsulfonyl,
ethylsulfonyl, trifluoromethylsulfonyl, allylsulfonyl,
propargylsulfonyl or dimethylsulfamoyl; R.sup.7 is hydrogen, methyl
or ethyl R.sup.8 is a C.sub.1-C.sub.6-alkyl group which can have
attached to it up to three of the following radicals: halogen,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio,
C.sub.1-C.sub.4-haloalkoxy,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkoxy,
C.sub.3-C.sub.7-cycloalkyl and/or phenyl; a
C.sub.5-C.sub.7-cycloalkyl group which can have attached to it up
to three C.sub.1-C.sub.4-alkyl groups; C.sub.3-C.sub.6-alkenyl or
C.sub.3-C.sub.6-alkynyl; R.sup.9 is a C.sub.1-C.sub.6-alkyl group
which can have attached to it one to three of the following
radicals: halogen, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-haloalkoxy,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkoxy- ,
C.sub.3-C.sub.7-cycloalkyl and/or phenyl; a
C.sub.5-C.sub.7-cycloalkyl group which can have attached to it one
to three C.sub.1-C4-alkyl groups; C.sub.3-C.sub.6-alkenyl or
C.sub.3-C.sub.6-alkynyl; R.sup.10 is hydrogen,
C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.6-alkyl, or together with
R.sup.11 is a C.sub.4-C.sub.6-alkylene chain in which one methylene
group can be replaced by an oxygen atom or a
C.sub.1-C.sub.4-alkylimino group; R.sup.11 is a
C.sub.1-C.sub.4-alkyl group which can have attached to it one to
four halogen or C.sub.1-C.sub.4-alkoxy radicals;
C.sub.3-C6-cycloalkyl n is 0-3 o is 1-2 Z N or CH, or their
environmentally compatible salts and b) a synergistically active
amount of at least one herbicidal compound selected from groups b1
to b41 b1 1,3,4-thiadiazoles: buthidazole, cyprazole b2 amides:
allidochlor (CDAA), benzoylprop-ethyl, bromobutide, chlorthiamid,
dimepiperate, dimethenamid, diphenamid, etobenzanid (benzchlomet),
flamprop-methyl, fosamin, isoxaben, monalide, naptalame, pronamid
(propyzamid), propanil b3 aminophosphoric acids: bilanafos,
(bialaphos), buminafos, glufosinate-ammonium, glyphosate, sulfosate
b4 aminotriazoles: amitrol b5 anilides: anilofos, mefenacet b6
aryloxyalkanoic acids: 2,4-D, 2,4-DB, clomeprop, dichlorprop,
dichlorprop-P, dichlorprop-P (2,4-DP-P), fenoprop (2,4,5-TP),
fluoroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide,
napropanilide, triclopyr b7 benzoic acids: chloramben, dicamba b8
benzothiadiazinones: bentazone b9 bleaches: clomazone
(dimethazone), diflufenican, fluorochloridone, flupoxam, fluridone,
pyrazolate, sulcotrione (chlormesulone) b10 carbamates: asulam,
barban, butylate, carbetamid, chlorbufam, chlorpropham, cycloate,
desmedipham, di-allate, EPTC, esprocarb, molinate, orbencarb,
pebulate, phenisopham, phenmedipham, propham, prosulfocarb,
pyributicarb, sulf-allate (CDEC), terbucarb, thiobencarb
(benthiocarb), tiocarbazil, tri-allate, vernolate b11
quinolinecarboxylic acids: quinclorac, quinmerac b12
chloracetanilides: acetochlor, alachlor, butachlor, butenachlor,
diethatyl-ethyl, dimethachlor, metazachlor, metolachlor,
pretilachlor, propachlor, prynachlor, terbuchlor, thenylchlor,
xylachlor b13 cyclohexenones: alloxydim, caloxydim, clethodim,
cloproxydim, cycloxydim, sethoxydim, tralkoxydim,
2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-
-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one b14
dichlorpropionic acids: dalapon b15 dihydrobenzofurans:
ethofumesate b16 dihydrofuran-3-ones: flurtamone b17
dinitroanilines: benefin, butralin, dinitramin, ethalfluralin,
fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin,
prodiamine, profluralin, trifluralin b18 dinitrophenols:
bromofenoxim, dinoseb, dinoseb-acetat, dinoterb, DNOC b19 diphenyl
ethers: acifluorfen-sodium, aclonifen, bifenox, chlornitrofen
(CNP), difenoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl,
fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen,
oxyfluorfen b20 dipyridylenes: cyperquat, difenzoquat
methylsulfate, diquat, paraquat dichloride b21 ureas:
benzthiazuron, buturon, chlorbromuron, chloroxuron, chlortoluron,
cumyluron, dibenzyluron, cycluron, dimefuron, diuron, dymrone,
ethidimuron, fenuron, fluometuron, isoproturon, isouron,
karbutilate, linuron, methabenzthiazuron, metobenzuron, metoxuron,
monolinuron, monuron, neburon, siduron, tebuthiuron, trimeturon b22
imidazoles: isocarbamid b23 imidazolinones: imazamethapyr,
imazapyr, imazaquin, imazethabenz-methyl (imazame), imazethapyr b24
oxadiazoles: methazole, oxadiargyl, oxadiazon b25 oxiranes:
tridiphane b26 phenols: bromoxynil, ioxynil b27
phenoxyphenoxypropionic esters: clodinafop, cyhalofop-butyl,
diclofopmethyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl,
fenthiapropethyl, fluazifop-butyl, fluazifop-P-butyl,
haloxyfopethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl,
isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-P-ethyl,
quizalofop-tefuryl b28 phenylacetic acids: chlorfenac (fenac) b29
phenylpropionic acid: chlorophenprop-methyl b30 protoporphyrinogen
IX oxydase inhibitors: benzofenap, cinidon-ethyl,
flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil,
fluthiacet-methyl, pyrazoxyfen, sulfentrazone, thidiazimin b31
pyrazoles: nipyraclofen b32 pyridazines: chloridazon, maleic
hydrazide, norflurazon, pyridate b33 pyridinecarboxylic acids:
clopyralid, dithiopyr, picloram, thiazopyr b34 pyrimidyl ethers:
pyrithiobac acid, pyrithiobac sodium, KIH-2023, KIH-6127 b35
sulfonamides: flumetsulam, metosulam b36 sulfonylureas:
amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl,
chlorsulfuron, cinosulfuron, cyclosulfamuron,
ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron,
halosulfuron-methyl, imazosulfuron, metsulfuron-methyl,
nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl,
rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl,
triasulfuron, tribenuron-methyl, triflusulfuron-methyl b37
triazines: ametryn, atrazine, aziprotryn, cyanazine, cyprazine,
desmetryn, dimethamethryn, dipropetryn, eglinazine-ethyl,
hexazinon, procyazine, prometon, prometryn, propazine, secbumeton,
simazine, simetryn, terbumeton, terbutryn, terbuthylazine,
trietazine b38 triazinones: ethiozin, metamitron, metribuzin b39
triazolecarboxamides: triazofenamid b40 uracils: bromacil, lenacil,
terbacil b41 others: benazolin, benfuresate, bensulide, benzofluor,
butamifos, cafenstrole, chlorthal-dimethyl (DCPA), cinmethylin,
dichlobenil, endothall, fluorbentranil, mefluidide, perfluidone,
piperophos or their environmentally compatible salts.
2. A herbicidal mixture as claimed in claim 1, comprising a
sulfonylurea of the formula I where R.sup.1 is CO.sub.2CH.sub.3,
CO.sub.2C.sub.2H.sub.5, CO.sub.2iC.sub.3H.sub.7, CF.sub.3,
CF.sub.2H, CH.sub.2CF.sub.3, CF.sub.2CF.sub.3, OSO.sub.2CH.sub.3,
OSO.sub.2N(CH.sub.3).sub.2, Cl, NO.sub.2,
SO.sub.2N(CH.sub.3).sub.2, SO.sub.2CH.sub.3,
SO.sub.2C.sub.2H.sub.5, and N(CH.sub.3)SO.sub.2CH.sub.3- , R.sup.2
is hydrogen, halogen or methyl, R.sup.3 is CF.sub.2H, OCF.sub.3,
OCF.sub.2Cl, CF.sub.3, or, if R.sup.1 is CO.sub.2CH.sub.3 and
R.sup.2 is simultaneously fluorine, R.sup.3 is Cl, or, if R.sup.1
is F.sub.3, CH.sub.2CF.sub.3 or CF.sub.2CF.sub.3, R.sup.3 is
methyl, R.sup.4 is OCH.sub.3, R.sup.5 is hydrogen and Z is N or
CH.
3. A herbicidal mixture as claimed in claim 1 or 2, comprising a
sulfonylurea of the formula I where R.sup.1 is halogen, a group
ER.sup.6, a group CO.sub.2R.sup.8, SO.sub.2CH.sub.3 or
SO.sub.2C.sub.2H.sub.5, R.sup.2 is hydrogen, R.sup.3 is F, R.sup.4
is OCF.sub.3, OCF.sub.2Cl, OCH.sub.3, R.sup.5 is hydrogen, R.sup.6
and R.sup.8 have the meanings given in claim 1 and Z is N or
CH.
4. A herbicidal mixture as claimed in any of claims 1 to 3,
comprising a sulfonylurea of the formula I where R.sup.1 is
CF.sub.3, R.sup.2 is hydrogen, R.sup.3 is CF.sub.3, R.sup.4 is
OCH.sub.3, R.sup.5 is hydrogen and Z is N.
5. A herbicidal mixture as claimed in any of claims 1 to 4,
comprising at least one herbicidal compound (b) from the group
consisting of bromobutide, dimethenamid, isoxaben, propanil,
glufosinate-ammonium, glyphosate, sulfosate, mefenacet,
2,4-D,2,4-DB, 2,4-DBEE, dichlorprop, dichlorprop-p (2,4-DP-P),
fluroxypyr, MCPA, mecoprop, mecoprop-p, dicamba, bentazone,
clomazone, diflufenican, sulcotrione, phenmedipham, thiobencarb,
quinclorac, quinmerac, acetochlor, alachlor, butachlor,
metazachlor, metolachlor, pretilachlor, butroxydim, clethodim,
cycloxydim, sethoxydim, tralkoxydim, caloxydim,
2-{1-[2-(4-chlorophenoxy)-
propyloxyi-mino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohe-
xen-1-one, pendimethalin, acifluorfen-sodium, bifenox,
fluoroglycofen-ethyl, fomesafen, lactofen, chlortoluron, cycluron,
dymrone, isoproturon, methabenzthiazuron, imazaquin,
imazethabenzmethyl, imazethapyr, bromoxynil, ioxynil, clodinafop,
cyhalofop-butyl, fenoxyprop-ethyl, fenoxaprop-p-ethyl,
haloxyfop-p-methyl, cinidon-ethyl, flumiclorac-pentyl, flumipropyn,
fluthiacet-methyl, pyridate, clopyralid, bispyribac-sodium,
KIH-8555, KUH-920, flumetsulam, metosulam, amidosulfuron,
azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron,
cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron,
galosulfuron-methyl, HOE-107925, imazosulfuron, metsulfuron-methyl,
nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl,
rimsulfuron, thifensulfuron-methyl, triasulfuron,
tribenuron-methyl, atrazine, cyanazine, terbutylazin, benazolin,
benfuresate, cafenstrole, cinmethylin, ammonium-bentazone,
cloquintocet, ET-751, F-8426, KPP-314.
6. A herbicidal mixture as claimed in any of claims 1 to 5,
comprising at least one herbicidal compound (b) from the group
consisting of 2,4-D, MCPA, dichlorprop-p, mecoprop-p, dicamba,
bentazone, diflufenican, sulcotrione, quinclorac, caloxydim,
cycloxydim, sethoxydim,
2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydro-
thiopyran-3-yl)-2-cyclohexen-1-one, acifluorfen-sodium,
fluoroglycofen-ethyl, bromoxynil, fenoxyprop-ethyl, cinidon-ethyl,
amidosulfuron, bensulfuron-methyl, metsulfuron-methyl,
nicosulfuron, pyrazosulfuron-ethyl, rimsulfuron, triasulfuron,
tribenuron-methyl, atrazine, terbuthylazine, ammonium-bentazone,
cloquintocet.
7. A herbicidal mixture as claimed in any of claims 1 to 6,
comprising a sulfonylurea (a) of the formula I and one or more
herbicidal compounds (b) in a weight ratio of 1:0.1 to 1:40.
8. A herbicidal mixture as claimed in claim 7, comprising a
sulfonylurea (a) of the formula I and one or more herbicidal
compounds (b) in a weight ratio of 1:0.2 to 1:20.
9. A herbicidal composition comprising a herbicidally active amount
of a sulfonylurea (a) of the formula I as claimed in any of claims
1 to 4, a synergistically active amount of at least one herbicidal
compound (b) as claimed in any of claims 1, 5 or 6, at least one
liquid and/or solid carrier and, if desired, at least one
adjuvant.
10. A herbicidal composition as claimed in claim 9, which comprises
the sulfonylurea (a) of the formula I and one or more herbicidal
compounds (b) in a weight ratio of 1:0.1 to 1:40.
11. A herbicidal composition as claimed in claim 9 or 10, which
comprises the sulfonylurea (a) of the formula I and one or more
herbicidal compounds (b) in a weight ratio of 1:0.2 to 1:20.
12. A method of controlling undesirable vegetation, which comprises
applying a sulfonylurea (a) of the formula I as set forth in any of
claims 1 to 4 and one or more herbicidal compounds (b) as set forth
in claim 1 before, during and/or after the emergence of undesirable
plants, either simultaneously or in succession.
13. A method of controlling undesirable vegetation, which comprises
treating the leaves of the crop plants and of the undesirable
plants with a sulfonylurea (a) of the formula I as set forth in any
of claims 1 to 4 and one or more compounds (b) as set forth in
claim 1, either simultaneously or in succession.
Description
[0001] The present invention relates to a synergistically active
herbicidal mixture composed of a sulfonylurea derivative (a) of the
formula I and one or more herbicidal compounds b1 to b41.
[0002] Herbicidally active sulfonylureas of the formula I have been
disclosed in the prior art, for example in EP-388 873, EP-559 814,
EP-291 851 and DE-40 07 683 and the Conference Proceedings
"Fluorine in Agriculture", Jan. 9-11 1995, Manchester, chapter "New
Fluoro Intermediates for Herbicidal Sulfonylureas".
[0003] Herbicidal compounds b1 to b41 are described, for example,
in "Herbizide", Hock, Fedtke, Schmidt, 1st Edition, Thieme 1995
(see "quinclorac" p. 238, "molinate" p. 32, "butachlor" p. 32,
"pretilachlor" p. 32, "dithiopyr" p. 32, "mefenacet" p. 32,
"fenoxapropethyl" p. 216, "dimepiperate" p. 32, "pyrazolate" p.
146, "pyrazoxyfen" p. 146, "bensulfuron-methyl p. 31,
"pyrazosulfuron-ethyl" p. 31, "cinosulfuron" p. 31, "benfuresate"
p. 233, "bromobutide" p. 243, "dymrone" p. 243, "dimethyametryn" p.
118, "esprocarb" p. 229, "pyributicarb" p. 32, "cinemthylin" p. 32,
"propanil" p. 32, "2,4-D" p. 30, "bentazone" p. 30, "DPX-A-8947" p.
175, "mecoprop-P" p. 237, "chlorpropham" p. 205, "thiocarbazil" p.
229, "ethoxyfen" p. 30, "haloxyfop-P-methyl" p. 38,
"haloxyfop-ethoxyethyl" p. 38, "flumiclorac-pentyl" p. 35,
"flupropacil" p. 143, "nipyraclofen" p. 145, "metosulam" p. 33,
"ethametsulfuron-methyl- " p. 36, "thifensulfuron-methyl" p. 35 or
in "Agricultural Chemicals", Book II Herbicides, 1993 see
"thiobencarb" p. 85, "benzofenap" p. 221, Inapropanilid" p. 49,
"piperophos" p. 102, "anilofos" p. 241, "TH-913" p. 150, "HW-52" p.
54, "ICIA-0051" p. 268, "poast" p. 253, "focus" p. 222,
"dimethenamid" p. 48, "sulfosate" p. 236, "2,4-DB" p. 10,
"dichlorprop-P" p. 6, "flupoxam" p. 44, "prosulfocarb" p. 84,
"quinmerac" p. 233, "metazachlorn" p. 64, "flurtamone" p. 265,
"bromofenoxim" p. 228, "fomesafen" p. 248, "imazethabenz-methyl" p.
153, "clodinafop" p. 214, "fenoxaprop-P-ethyl" p. 208,
"fluazifop-P-butyl" p. 207, "quizalofop-P-ethyl" p. 210,
"quizalofop-terfuryl" p. 211, "flumioxazin" p. 43, "flumipropyn" p.
267, "sulfentrazone" p. 261, "thiazopyr" p. 226,
"pyrithiobac-sodium" p. 266, "flumetsulam" p. 227, "amidosulfuron"
p. 151, "halosulfuron-methyl" p. 148, "rimsulfuron" p. 138,
"tribenuron-methyl" p. 139, "triflusulfuron-methyl" p. 137,
"primisulfuron" p. 147 or in "Short Review of Herbicides & PGRs
1991, Hodogaya Chemicals see "furyloxyfen" p. 142, "triazofenamid"
p. 268, "KH-218" p. 52, "NSK-850" p. 52, "JC-940" p.90, "AC-92553"
p. 58, "buthidazole" p. 88, "cyprazole" p.38, "allidochlor" p. 48,
"benzoylprop-ethyl" 5 p. 38, "chlorthiamid" p. 150, "diphenamid" p.
34, "flamprop-methyl" p. 40, "fosamin" p. 232, "isoxaben" p. 42,
"monalide" p. 32, "naptalam" p. 36, "pronamid" p. 34, "bialaphos"
p. 234, "glufosinate-ammonium" p. 234, "glyphosaten p." 232,
"aamitrol" p. 254, "clomeprop" p. 20, "dichlorprop" p. 6,
"fenoprop" p. 8, "fluroxypyr" p. 156, "MCPA" p. 4, "MCPB" p. 8,
"mecoprop" p. 6, "napropamide" p. 16, "triclopyr" p. 154,
"chloramben" p. 28, "dicamba" p. 26, "clomazone" p. 268,
"diflufenican" p. 42, "fluorochloridone" p. 266, "fluridone" p.
156, "asulam" p. 112, "barban" p. 100, "butylate" p. 106,
"carbetamide" p. 36, "chlorobufam" p. 100, "cycloate" p. 108,
"desmedipham" p. 104, "di-allate" p. 106, "EPTC" p. 108,
"orbencarb" p. 112, "pebulate" p. 106, "phenisopham" p. 118,
"pendimedipham" p. 104, "propham" p. 100, "sulf-allate" p. 110,
"terbucarb" p. 102, "tri-allate" p. 108, "vernolate" p. 108,
"acetochlor" p. 48, "alachlor" p. 46, "diethathyl-ethyl" p. 48,
"dimethachlor" p. 50, "metolachlor" p. 46, "propachlor" p. 44,
"pyrnachlor" p. 44, "terbuchlor" p. 48, "xylachlor" p. 52,
"alloxydim" p. 260, "clethodim" p. 270, "cloproxydimo p. 268,
"tralkoxydim" p. 270, "dalapon" p. 212, "ethofumesate" p. 124,
"benefin" p. 54, "butralin" p. 58, "dinitramin" p. 56,
"ethalfluralin" p. 60, "fluchloralin" p. 54, "isopropalin" p. 58,
"nitralin" p. 58, "oryzalin" p. 60, "prodiamine" p. 62,
"profluralin" p. 54, "trifluralin" p. 54, "dinoseb" p. 128,
"dinoseb-acetate" p. 128, "dinoterb" p. 128, "DNOC" p. 126,
"acilfluorfen-sodium" p. 142, "aclonifen" p. 146, "bifenox" p. 140,
"chlornitrofen" p. 138, "difenoxuron" p. 76, "fluorodifen" p. 138,
"fluoroglycofen-ethyl" p. 146, "lactofen" p. 144, "nitrofen" p.
136, "nitrofluorfen" p. 140, "oxyfluorfen" p. 140, "cyperquat" p.
158, "difenzoquat" p. 160, "diquat" p. 158, "paraquat" p. 158,
"benzthiazuron" p. 82, "buturon" p. 66, "chlorbromuron" p. 72,
"chloroxuron" p. 76, "chlortoluron" p. 74, "cycluron" p. 84,
"dimeturon" p. 88, "diuron" p. 70, "ethidimuron" p. 86, "fenuron"
p. 64, "fluometuron" p. 68, "isoproturon" p. 80, "isouron" p. 88,
"karbutilate" p. 76, "linuron" p. 72, "methabenzthiazuron" p. 82,
"metoxuron" p. 72, "monolinuron" p. 66, "monuron" p. 64, "neburon"
p. 72, "siduron" p. 68, "tebuthiuron" p. 86, "trimeturon" p. 64,
"isocarbamid" p. 168, "imazamethapyr" p. 172, "imazapyr" p. 170,
"imazaquin" p. 170, "imazethapyr" p. 172, "methazole" p. 162,
"oxadiazon" p. 162, "tridiphane" p. 266, "bromoxynil" p. 148,
"ioxynil" p. 148, "diclofop-methyl" p. 16, "fenthiaprop-ethyl" p.
20, "fluazifop-butyl" p. 18, "haloxyfop-methyl" p. 18,
"isoxapyrifop" p. 22, "propaquizafop" p. 24, "quizalofop-ethyl" p.
20, "chlorfenac" p. 258, "chlorophenprop-methyl" p. 258,
"chloridazon" p. 174, "maleic hydrazide" p. 162, "norflurazon" p.
174, "pyridate" p. 176, "clopyralid" p. 154, "picloram" p. 154,
"chlorimuron-ethyl" p. 92, "chlorsulfuron" p. 92, "flazasulfuron"
p. 96, "metsulfuron-methyl" p. 92, "nicosulfuron" p. 96,
"sulfometuron-methyl" p. 92, "triasulfuron" p. 94, "ametryn" p.
198, "atrazine" p. 188, "aziprotryne" p. 206, "cyanazine" p. 192,
"cyprazine" p. 192, "desmetryne" p. 200, "dipropetryn" p. 202,
"eglinazine-ethyl" p. 208, "hexazinon" p. 208, procyazine" p. 192,
"prometone" p. 196, "prometryn" p. 196, "propazine" p. 188,
"secbumeton" p. 196, "simazine" p. 188, "simetryn" p. 196,
"terbumeton" p. 204, "terbutryn" p. 198, "terbuthylazine" p. 190,
"trietazine" p. 188, "ethiozin" p. 210, "metamitron" p. 206,
"metribuzin" p. 202, "bromacil" p. 180, "lenacil" p. 180,
"terbacil" p. 180, "benazolin" p. 262, "bensulide" p. 228,
"benzofluor" p. 266, "butamifos" p. 228, "DCPA" p. 28,
"dichlobenil" p. 148, "endothal" p. 264, "mefluididen" p. 306,
"perfluidone" p. 260, "terbuchlor" p. 48 or in "Global Herbicide
Directory" First Edition, 1994 see "oxadiargyl" p. 96, or in
"European Directory of Agrochemical Products Volume 2--Herbicides"
Fourth Edition, see "buminafos" p. 255. The compound "DEH-112" is
disclosed in European Patent Application EP 0 302 203. The compound
"caloxydim" is described in DE 3 336 140, the compound
"cinidon-ethyl" in DE 3 603 789 and the compound "fluorbentranil"
in EP 84 893. Other-compounds are known from "Brighton Crop
Protection Conference--Weeds--1993 (see "thidiazimin" p. 29,
"AC-322140" p. 41, "KIH-6127" p. 47, "prosulfuron" p. 53,
"KIH-2023" p. 61, "metobenzuron" p. 67). The compound "CH-900" is
described in EP 0 332 133.
[0004] In principle, it is desirable in crop protection products to
increase the specific activity of an active ingredient and the
reliability of its action. It was therefore the object of the
present invention to increase the activity of known, herbicidally
active-sulfonylureas of the formula I.
[0005] We have found that this object is achieved by a herbicidal
mixture which comprises
[0006] a) at least one derivative of the sulfonylurea of the
formula I 2
[0007] where the substituents have the following meanings:
[0008] R.sup.1 is C.sub.1-C.sub.6-alkyl which has attached to it
one to five of the following groups: methoxy, ethoxy,
SO.sub.2CH.sub.3, cyano, chlorine, fluorine, SCH.sub.3,
S(O)CH.sub.3;
[0009] halogen;
[0010] a group ER.sup.6 where E is O, S or NR.sup.7;
[0011] COOR.sup.8;
[0012] NO.sub.2;
[0013] S(O).sub.oR.sup.9, SO.sub.2NR.sup.10R.sup.11,
CONR.sup.10R.sup.11;
[0014] R.sup.2 is hydrogen, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl- , C.sub.2-C.sub.4-alkynyl, halogen,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy;
C.sub.1-C.sub.4-haloalkyl, a C.sub.1-C.sub.2-alkylsulfonyl group,
nitro, cyano or C.sub.1-C.sub.4-alkylthio;
[0015] R.sup.3 is F, CF.sub.3, CF.sub.2Cl, CF.sub.2H, OCF.sub.3,
OCF.sub.2Cl, or, if R.sup.1 is CO.sub.2CH.sub.3 and R.sup.2 is
simultaneosly fluorine, R.sup.3 is Cl, or, if R.sup.1 is
CH.sub.2CF.sub.3 or CF.sub.2CF.sub.3, R.sup.3 is methyl, or, if
R.sup.4 is OCF.sub.3 or OCF.sub.2Cl, R.sup.3 is OCF.sub.2H or
OCF.sub.2Br;
[0016] R.sup.4 is C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.2-alkylthio, C.sub.1-C.sub.2-alkylamino,
di-C.sub.1-C.sub.2-alkylamino, halogen, C.sub.1-C.sub.2-haloalkyl,
C.sub.1-C.sub.2-haloalkoxy,
[0017] R.sup.5 is hydrogen, C.sub.1-C.sub.2-alkoxy,
C.sub.1-C.sub.4-alkyl;
[0018] R.sup.6 is C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl or C.sub.3-C.sub.6-cycloalkyl, all of which
can have attached to them 1 to 5 halogen atoms, with the exception
of allyl, difluoromethoxy, chlorodifluoromethoxy and
2-chloroethoxy, if E is O or S. In the event that E is O or
NR.sup.7, R.sup.6 is furthermore also methylsulfonyl,
ethylsulfonyl, trifluoromethylsulfonyl, allylsulfonyl,
propargylsulfonyl or dimethylsulfamoyl;
[0019] R.sup.7 is hydrogen, methyl or ethyl
[0020] R.sup.8 is a C.sub.1-C.sub.6-alkyl group which can have
attached to it up to three of the following radicals: halogen,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio,
C.sub.1-C.sub.4-haloalkoxy,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkoxy- ,
C.sub.3-C.sub.7-cycloalkyl and/or phenyl; a
C.sub.5-C.sub.7-cycloalkyl group which can have attached to it up
to three C.sub.1-C.sub.4-alkyl groups; C.sub.3-C.sub.6-alkenyl or
C.sub.3-C.sub.6-alkynyl;
[0021] R.sup.9 is a C.sub.1-C.sub.6-alkyl group which can have
attached to it one to three of the following radicals; halogen,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio,
C.sub.1-C.sub.4-haloalkoxy,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkoxy- ,
C.sub.3-C.sub.7-cycloalkyl and/or phenyl; a
C.sub.5-C.sub.7-cycloalkyl group which can have attached to it one
to three C.sub.1-C.sub.4-alkyl groups; a C.sub.3-C.sub.6-alkenyl
group or a C.sub.3-C.sub.6-alkynyl group;
[0022] R.sup.10 is hydrogen, a C.sub.1-C.sub.2-alkoxy group, a
C.sub.1-C.sub.6-alkyl group, or together with R.sup.11 is a
C.sub.4-C.sub.6-alkylene chain in which one methylene group can be
replaced by an oxygen atom or a C.sub.1-C.sub.4-alkylimino
group;
[0023] R.sup.11 is a C.sub.1-C.sub.4-alkyl group which can have
attached to it one to four halogen or C.sub.1-C.sub.4-alkoxy
radicals; C.sub.3-C.sub.6-cycloalkyl
[0024] n is 0-3
[0025] o is 1-2
[0026] Z N or CH, and
[0027] b) a synergistically active amount of at least one
herbicidal compound selected from the groups b1 to b41
[0028] b1 1,3,4-thiadiazoles:
[0029] buthidazole, cyprazole
[0030] b2 amides:
[0031] allidochlor (CDAA), benzoylprop-ethyl, bromobutide,
chlorthiamid, dimepiperate, dimethenamid, diphenamid, etobenzanid
(benzchlomet), flamprop-methyl, fosamin, isoxaben, monalide,
naptalame, pronamid (propyzamid), propanil
[0032] b3 aminophosphoric acids:
[0033] bilanafos, (bialaphos), buminafos, glufosinate-ammonium,
glyphosate, sulfosate
[0034] b4 aminotriazoles:
[0035] amitrol
[0036] b5 anilides:
[0037] anilofos, mefenacet
[0038] b6 aryloxyalkanoic acids:
[0039] 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P,
dichlorprop-P (2,4-DP-P), fenoprop (2,4,5-TP), fluoroxypyr, MCPA,
MCPB, mecoprop, mecoprop-P, napropamide, napropanilide,
triclopyr
[0040] b7 benzoic acids:
[0041] chloramben, dicamba
[0042] b8 benzothiadiazinones:
[0043] bentazone
[0044] b9 bleaches:
[0045] clomazone (dimethazone), diflufenican, fluorochloridone,
flupoxam, fluridone, pyrazolate, sulcotrione (chlormesulone)
[0046] b10 carbamates:
[0047] asulam, barban, butylate, carbetamid, chlorbufam,
chlorpropham, cycloate, desmedipham, di-allate, EPTC, esprocarb,
molinate, orbencarb, pebulate, phenisopham, phenmedipham, propham,
prosulfocarb, pyributicarb, sulf-allate (CDEC), terbucarb,
thiobencarb (benthiocarb), tiocarbazil, tri-allate, vernolate
[0048] b11 quinolinecarboxylic acids:
[0049] quinclorac, quinmerac
[0050] b12 chloracetanilides:
[0051] acetochlor, alachlor, butachlor, butenachlor,
diethatylethyl, dimethachlor, metazachlor, metolachlor,
pretilachlor, propachlor, prynachlor, terbuchlor, thenylchlor,
xylachlor
[0052] b13 cyclohexenones:
[0053] alloxydim, caloxydim, clethodim, cloproxydim, cycloxydim,
sethoxydim, tralkoxydim,
2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-
-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one
[0054] b14 dichloropropionic acids:
[0055] dalapon
[0056] b15 dihydrobenzofurans:
[0057] ethofumesate
[0058] b16 dihydrofuran-3-ones:
[0059] flurtamone
[0060] b17 dinitroanilines:
[0061] benefin, butralin, dinitramin, ethalfluralin, fluchloralin,
isopropalin, nitralin, oryzalin, pendimethalin, prodiamine,
profluralin, trifluralin
[0062] b18 dinitrophenols:
[0063] bromofenoxim, dinoseb, dinoseb-acetate, dinoterb, DNOC
[0064] b19 diphenyl ethers:
[0065] acifluorfen-sodium, aclonifen, bifenox, chlornitrofen (CNP),
difenoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl,
fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen,
oxyfluorfen
[0066] b20 dipyridylenes:
[0067] cyperquat, difenzoquat methylsulfate, diquat, paraquat
dichloride
[0068] b21 ureas:
[0069] benzthiazuron, buturon, chlorbromuron, chloroxuron,
chlortoluron, cumyluron, dibenzyluron, cycluron, dimefuron, diuron,
dymrone, ethidimuron, fenuron, fluometuron, isoproturon, isouron,
karbutilate, linuron, methabenzthiazuron, metobenzuron, metoxuron,
monolinuron, monuron, neburon, siduron, tebuthiuron, trimeturon
[0070] b22 imidazoles:
[0071] isocarbamid
[0072] b23 imidazolinones:
[0073] imazamethapyr, imazapyr, imazaquin, imazethabenz-methyl
(imazame), imazethapyr
[0074] b24 oxadiazoles:
[0075] methazole, oxadiargyl, oxadiazon
[0076] b25 oxiranes:
[0077] tridiphane
[0078] b26 phenols:
[0079] bromoxynil, ioxynil
[0080] b27 phenoxyphenoxypropionic esters:
[0081] clodinafop, cyhalofop-butyl, diclofop-methyl,
fenoxapropethyl, fenoxaprop-P-ethyl, fenthiapropethyl,
fluazifopbutyl, fluazifop-P-butyl, haloxyfop-ethoxyethyl,
haloxyfop-methyl, halofopop-P-methyl, isoxapyrifop, propaquizafop,
quizalofop-ethyl, quizalofop-P-ethyl, quizalofoptefuryl
[0082] b28 phenylacetic acids:
[0083] chlorfenac (fenac)
[0084] b29 phenylpropionic acid:
[0085] chlorophenprop-methyl
[0086] b30 protoporphyrinogen IX oxydase inhibitors:
[0087] benzofenap, cinidon-ethyl, flumiclorac-pentyl, flumioxazin,
flumipropyn, flupropacil, fluthiacet-methyl, pyrazoxyfen,
sulfentrazone, thidiazimin
[0088] b31 pyrazoles:
[0089] nipyraclofen
[0090] b32 pyridazines:
[0091] chloridazon, maleic hydrazide, norflurazon, pyridate
[0092] b33 pyridinecarboxylic acids:
[0093] clopyralid, dithiopyr, picloram, thiazopyr
[0094] b34 pyrimidyl ethers:
[0095] pyrithiobac acid, pyrithiobac sodium, KIH-2023, KIH-6127
[0096] b35 sulfonamides:
[0097] flumetsulam, metosulam
[0098] b36 sulfonylureas:
[0099] amidosulfuron, azimsulfuron, bensulfuron-methyl,
chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron,
ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron,
halosulfuron-methyl, imazosulfuron, metsulfuron-methyl,
nicosulfuron, primisulfuron, prosulfuron, pyrazo-sulfuron-ethyl,
rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl,
triasulfuron, tribenuron-methyl, triflusulfuron-methyl
[0100] b37 triazines:
[0101] ametryn, atrazine, aziprotryn, cyanazine, cyprazine,
desmetryn, dimethamethryn, dipropetryn, eglinazine-ethyl,
hexazinon, procyazine, prometon, prometryn, propazine, secbumeton,
simazine, simetryn, terbumeton, terbutryn, terbuthylazine,
trietazine
[0102] b38 triazinones:
[0103] ethiozin, metamitron, metribuzin
[0104] b39 triazolecarboxamides:
[0105] triazofenamid
[0106] b40 uracils:
[0107] bromacil, lenacil, terbacil
[0108] b41 others:
[0109] benazolin, benfuresate, bensulide, benzofluor, butamifos,
cafenstrole, chlorthal-dimethyl (DCPA), cinmethylin, dichlobenil,
endothall, fluorbentranil, mefluidide, perfluidone, piperophos
[0110] or their environmentally compatible salts.
[0111] The herbicidal mixture according to the invention has
superadditive synergistic action and is selective for those crop
plants which also tolerate the individual compounds themselves.
[0112] Especially preferred sulfonylureas of the formula I with a
view to their synergistic herbicidal action are those where
[0113] R.sup.1 is CO.sub.2CH.sub.3, CO.sub.2C.sub.2H.sub.5,
CO.sub.2iC.sub.3H.sub.7, CF.sub.3, CF.sub.2H; OSO.sub.2CH.sub.3,
OSO.sub.2N(CH.sub.3).sub.2, Cl, NO.sub.2,
SO.sub.2N(CH.sub.3).sub.2, SO.sub.2CH.sub.3 and
N(CH.sub.3)SO.sub.2CH.sub.3
[0114] R.sup.2 is hydrogen, Cl, F or C.sub.1-C.sub.2-alkyl
[0115] R.sup.3 is CF.sub.2H, OCF.sub.3, OCF.sub.2Cl, CF.sub.2Cl,
CF.sub.3 or F
[0116] R.sup.4 is OCH.sub.3, OC.sub.2H.sub.5, OCF.sub.3,
OCF.sub.2Cl; CF.sub.3, Cl, F, NH(CH.sub.3), N(CH.sub.3).sub.2 or
C.sub.1-C.sub.2-alkyl
[0117] R.sup.5 is hydrogen,
[0118] Z is N or CH and
[0119] 0 or 1.
[0120] Preferred compounds of the formula I are compiled in the
table which follows.
1TABLE 3 No. R.sup.1 R.sup.2 R.sup.5 R.sup.3 R.sup.4 Z 1
CO.sub.2CH.sub.3 H H OCF.sub.2Cl OCH.sub.3 CH 2
CO.sub.2C.sub.2H.sub.5 H H OCF.sub.2Cl OCH.sub.3 CH 3
CO.sub.2iC.sub.3H.sub.7 H H OCF.sub.2Cl OCH.sub.3 CH 4 NO.sub.2 H H
OCF.sub.2Cl OCH.sub.3 CH 5 SO.sub.2CH.sub.3 H H OCF.sub.2Cl
OCH.sub.3 CH 6 SO.sub.2N(CH.sub.3).sub.2 H H OCF.sub.2Cl OCH.sub.3
CH 7 Cl H H OCF.sub.2Cl OCH.sub.3 CH 8 N(CH.sub.3)SO.sub.2CH.sub.3
H H OCF.sub.2Cl OCH.sub.3 CH 9 OSO.sub.2CH.sub.3 H H OCF.sub.2Cl
OCH.sub.3 CH 10 OSO.sub.2N(CH.sub.3).sub.2 H H OCF.sub.2Cl
OCH.sub.3 CH 11 CF.sub.3 H H OCF.sub.2Cl OCH.sub.3 CH 12 CF.sub.2H
H H OCF.sub.2Cl OCH.sub.3 CH 13 CO.sub.2CH.sub.3 H H OCF.sub.3
OCH.sub.3 CH 14 CO.sub.2C.sub.2H.sub.5 H H OCF.sub.3 OCH.sub.3 CH
15 CO.sub.2iC.sub.3H.sub.7 H H OCF.sub.3 OCH.sub.3 CH 16 NO.sub.2 H
H OCF.sub.3 OCH.sub.3 CH 17 SO.sub.2CH.sub.3 H H OCF.sub.3
OCH.sub.3 CH 18 SO.sub.2N(CH.sub.3).sub.2 H H OCF.sub.3 OCH.sub.3
CH 19 Cl H H OCF.sub.3 OCH.sub.3 CH 20 N(CH.sub.3)SO.sub.2CH.sub.3
H H OCF.sub.3 OCH.sub.3 CH 21 OSO.sub.2CH.sub.3 H H OCF.sub.3
OCH.sub.3 CH 22 OSO.sub.2N(CH.sub.3).sub.2 H H OCF.sub.3 OCH.sub.3
CH 23 CF.sub.3 H H OCF.sub.3 OCH.sub.3 CH 24 CF.sub.2H H H
OCF.sub.3 OCH.sub.3 CH 25 CO.sub.2CH.sub.3 H H F OCH.sub.3 CH 26
CO.sub.2C.sub.2H.sub.5 H H F OCH.sub.3 CH 27
CO.sub.2iC.sub.3H.sub.7 H H F OCH.sub.3 CH 28 NO.sub.2 H H F
OCH.sub.3 CH 29 SO.sub.2CH.sub.3 H H F OCH.sub.3 CH 30
SO.sub.2N(CH.sub.3).sub.2 H H F OCH.sub.3 CH 31 Cl H H F OCH.sub.3
CH 32 N(CH.sub.3)SO.sub.2CH.sub.3 H H F OCH.sub.3 CH 33
OSO.sub.2CH.sub.3 H H F OCH.sub.3 CH 34 OSO.sub.2N(CH.sub.3).sub.2
H H F OCH.sub.3 CH 35 CF.sub.3 H H F OCH.sub.3 CH 36 CF.sub.2H H H
F OCH.sub.3 CH 37 CO.sub.2CH.sub.3 H H CF.sub.3 OCH.sub.3 N 38
CO.sub.2C.sub.2H.sub.5 H H CF.sub.3 OCH.sub.3 N 39
CO.sub.2iC.sub.3H.sub.7 H H CF.sub.3 OCH.sub.3 N 40 NO.sub.2 H H
CF.sub.3 OCH.sub.3 N 41 SO.sub.2CH.sub.3 H H CF.sub.3 OCH.sub.3 N
42 SO.sub.2N(CH.sub.3).sub.2 H H CF.sub.3 OCH.sub.3 N 43 Cl H H
CF.sub.3 OCH.sub.3 N 44 N(CH.sub.3)SO.sub.2CH.sub- .3 H H CF.sub.3
OCH.sub.3 N 45 OSO.sub.2CH.sub.3 H H CF.sub.3 OCH.sub.3 N 46
OSO.sub.2N(CH.sub.3).sub.2 H H CF.sub.3 OCH.sub.3 N 47 CF.sub.3 H H
CF.sub.3 OCH.sub.3 N 48 CF.sub.2H H H CF.sub.3 OCH.sub.3 N 49
CO.sub.2CH.sub.3 H H CF.sub.3 OCH.sub.3 CH 50
CO.sub.2C.sub.2H.sub.5 H H CF.sub.3 OCH.sub.3 CH 51
CO.sub.2iC.sub.3H.sub.7 H H CF.sub.3 OCH.sub.3 CH 52 NO.sub.2 H H
CF.sub.3 OCH.sub.3 CH 53 SO.sub.2CH.sub.3 H H CF.sub.3 OCH.sub.3 CH
54 SO.sub.2N(CH.sub.3).sub.2 H H CF.sub.3 OCH.sub.3 CH 55 Cl H H
CF.sub.3 OCH.sub.3 CH 56 N(CH.sub.3)SO.sub.2CH.sub.3 H H CF.sub.3
OCH.sub.3 CH 57 OSO.sub.2CH.sub.3 H H CF.sub.3 OCH.sub.3 CH 58
OSO.sub.2N(CH.sub.3).sub.2 H H CF.sub.3 OCH.sub.3 CH 59 CF.sub.3 H
H CF.sub.3 OCH.sub.3 CH 60 CF.sub.2H H H CF.sub.3 OCH.sub.3 CH 61
CO.sub.2CH.sub.3 H H CF.sub.2H OCH.sub.3 N 62
CO.sub.2C.sub.2H.sub.5 H H CF.sub.2H OCH.sub.3 N 63
CO.sub.2iC.sub.3H.sub.7 H H CF.sub.2H OCH.sub.3 N 64 NO.sub.2 H H
CF.sub.2H OCH.sub.3 N 65 SO.sub.2CH.sub.3 H H CF.sub.2H OCH.sub.3 N
66 SO.sub.2N(CH.sub.3).sub.2 H H CF.sub.2H OCH.sub.3 N 67 Cl H H
CF.sub.2H OCH.sub.3 N 68 N(CH.sub.3)SO.sub.2CH.sub.3 H H CF.sub.2H
OCH.sub.3 N 69 OSO.sub.2CH.sub.3 H H CF.sub.2H OCH.sub.3 N 70
OSO.sub.2N(CH.sub.3).sub.2 H H CF.sub.2H OCH.sub.3 N 71 CF.sub.3 H
H CF.sub.2H OCH.sub.3 N 72 CF.sub.2H H H CF.sub.2H OCH.sub.3 N 73
CO.sub.2CH.sub.3 H H CF.sub.2H OCH.sub.3 CH 74 CO.sub.2C.sub.2H5 H
H CF.sub.2H OCH.sub.3 CH 75 CO.sub.2iC.sub.3H.sub.7 H H CF.sub.2H
OCH.sub.3 CH 76 NO.sub.2 H H CF.sub.2H OCH.sub.3 CH 77
SO.sub.2CH.sub.3 H H CF.sub.2H OCH.sub.3 CH 78
SO.sub.2N(CH.sub.3).sub.2 H H CF.sub.2H OCH.sub.3 CH 79 Cl H H
CF.sub.2H OCH.sub.3 CH 80 N(CH.sub.3)SO.sub.2CH.sub.3 H H CF.sub.2H
OCH.sub.3 CH 81 OSO.sub.2CH.sub.3 H H CF.sub.2H OCH.sub.3 CH 82
OSO.sub.2N(CH.sub.3).sub.2 H H CF.sub.2H OCH.sub.3 CH 83 CF.sub.3 H
H CF.sub.2H OCH.sub.3 CH 84 CF.sub.2H H H CF.sub.2H OCH.sub.3 CH 85
CO.sub.2CH.sub.3 H H CF.sub.2Cl OCH.sub.3 N 86 CO.sub.2C2H.sub.5 H
H CF.sub.2Cl OCH.sub.3 N 87 CO.sub.2iC.sub.3H.sub.7 H H CF.sub.2Cl
OCH.sub.3 N 88 NO.sub.2 H H CF.sub.2Cl OCH.sub.3 N 89
SO.sub.2CH.sub.3 H H CF.sub.2Cl OCH.sub.3 N 90
SO.sub.2N(CH.sub.3).sub.2 H H CF.sub.2Cl OCH.sub.3 N 91 Cl H H
CF.sub.2Cl OCH.sub.3 N 92 N(CH.sub.3)SO.sub.2CH.sub.3 H H
CF.sub.2Cl OCH.sub.3 N 93 OSO.sub.2CH.sub.3 H H CF.sub.2Cl
OCH.sub.3 N 94 OSO.sub.2N(CH.sub.3).sub.2 H H CF.sub.2Cl OCH.sub.3
N 95 CF.sub.3 H H CF.sub.2Cl OCH.sub.3 N 96 CF.sub.2H H H
CF.sub.2Cl OCH.sub.3 N 97 CO.sub.2CH.sub.3 3-F H Cl OCH.sub.3 CH 98
CF.sub.2CF.sub.3 H H CH.sub.3 OCH.sub.3 N 99 CF.sub.2CF.sub.3 H H
CH.sub.3 OCH.sub.3 N 100 SO.sub.2C.sub.2H.sub.5 H H F OCH.sub.3
CH
[0121] Examples of preferred compounds (b) are
[0122] bromobutide
[0123] dimethenamid
[0124] isoxaben
[0125] propanil
[0126] glufosinate-ammonium
[0127] glyphosate
[0128] sulfosate
[0129] mefenacet
[0130] 2,4-D
[0131] 2,4-DB
[0132] 2,4-DBEE
[0133] dichlorprop
[0134] dichlorprop-P
[0135] dichlorprop-P (2,4-DP-P)
[0136] fluroxypyr
[0137] MCPA
[0138] mecoprop
[0139] mecoprop-P
[0140] dicamba
[0141] bentazone
[0142] clomazone
[0143] diflufenican
[0144] sulcotrione
[0145] phenmedipham
[0146] thiobencarb
[0147] quinclorac
[0148] quinmerac
[0149] acetochlor
[0150] alachlor
[0151] butachlor
[0152] metazachlor
[0153] metolachlor
[0154] pretilachlor
[0155] butroxydim
[0156] caloxydim
[0157] clethodim
[0158] cycloxydim
[0159] sethoxydim
[0160] tralkoxydim
[0161]
2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetr-
ahydrothiopyran-3-yl)-2-cyclohexen-1-one
[0162] pendimethalin
[0163] acifluorfen-sodium
[0164] bifenox
[0165] fluoroglycofen-ethyl
[0166] fomesafen
[0167] lactofen
[0168] chlortoluron
[0169] cycluron
[0170] dymrone
[0171] isoproturon
[0172] methabenzthiazuron
[0173] imazaquin
[0174] imazethabenz-methyl
[0175] imazethapyr
[0176] bromoxynil
[0177] ioxynil
[0178] clodinafop
[0179] cyhalofop-butyl
[0180] fenoxyprop-ethyl
[0181] fenoxaprop-P-ethyl
[0182] haloxyfop-P-methyl
[0183] cinidon-ethyl
[0184] flumiclorac-pentyl
[0185] flumipropyn
[0186] fluthiacet-methyl
[0187] pyridate
[0188] clopyralid
[0189] bispyribac-sodium
[0190] KIH-8555
[0191] KUH-920
[0192] flumetsulam
[0193] metosulam
[0194] amidosulfuron
[0195] azimsulfuron
[0196] bensulfuron-methyl
[0197] chlorimuron-ethyl
[0198] chlorsulfuron
[0199] cinosulfuron
[0200] cyclosulfamuron
[0201] ethoxysulfuron
[0202] flazasulfuron
[0203] halosulfuron-methyl
[0204] HOE-107925
[0205] imazosulfuron
[0206] metsulfuron-methyl
[0207] nicosulfuron
[0208] primisulfuron
[0209] prosulfuron
[0210] pyrazosulfuron-ethyl
[0211] rimsulfuron
[0212] thifensulfuron-methyl
[0213] triasulfuron
[0214] tribenuron-methyl
[0215] atrazine
[0216] cyanazine
[0217] terbuthylazine
[0218] benazolin
[0219] benfuresate
[0220] cafenstrole
[0221] cinemthylin
[0222] ammonium-bentazone
[0223] cloquintocet
[0224] ET-751
[0225] F-8426
[0226] KPP-314
[0227] The following compounds are particularly preferred:
[0228] 2,4-D
[0229] dichlorprop-P
[0230] MCPA
[0231] mecoprop-P
[0232] dicamba
[0233] bentazone
[0234] diflufenican
[0235] sulcotrione
[0236] quinclorac
[0237] caloxydim
[0238] cycloxydim
[0239] sethoxydim
[0240]
2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetr-
ahydrothiopyran-3-yl)-2-cyclohexen-1-one
[0241] acifluorfen-sodium
[0242] fluoroglycofen-ethyl
[0243] bromoxynil
[0244] fenoxyprop-ethyl
[0245] cinidon-ethyl
[0246] amidosulfuron
[0247] bensulfuron-methyl
[0248] metsulfuron-methyl
[0249] nicosulfuron
[0250] pyrazosulfuron-ethyl
[0251] rimsulfuron
[0252] triasulfuron
[0253] tribenuron-methyl
[0254] atrazine
[0255] terbuthylazine
[0256] ammonium-bentazone
[0257] cloquintocet
[0258] The following compounds are very especially preferred:
[0259] dichlorprop-P
[0260] mecoprop-P
[0261] ammonium-bentazone
[0262] bentazone
[0263] diflufenican
[0264] quinclorac
[0265]
2-(1-[2-(4-chlorophenoxy)propyloxyimino]butyl)-3-hydroxy-5-(2H-tetr-
ahydrothiopyran-3-yl)-2-cyclohexen-1-one
[0266] caloxydim
[0267] cycloxydim
[0268] sethoxydim
[0269] fluoroglycofen-ethyl
[0270] cinidon-ethyl
[0271] nicosulfuron
[0272] pyrazosulfuron-ethyl
[0273] rimsulfuron
[0274] atrazine
[0275] terbuthylazine.
[0276] The present invention also relates to herbicidal
compositions which comprise at least one herbicidally active amount
of a sulfonylurea (a) of the above-described formula I or their
environmentally compatible salts, a synergistically active amount
of at least one above-described herbicidal compound (b) or its
environmentally compatible salts, at least one liquid and/or solid
carrier and, if desired, at least one adjuvant.
[0277] In the herbicidal mixtures and herbicidal compositions
according to the invention, the sulfonylureas of the formula I or
their environmentally compatible salts and the herbicidal compounds
(b) or their environmentally compatible salts are used in such
weight ratios that the desired synergistic effect is observed. The
mixing ratios of sulfonylurea of the formula I and a herbicidal
compound (b) are preferably 1 to 1:0.1 to 1:40, in particular 1:0.2
to 1:20, especially preferably 1:0.5 to 1:15.
[0278] The herbicidal mixtures and herbicidal compositions
according to the invention which comprise the sulfonylureas of the
formula I or their environmentally compatible salts of, for
example, alkali metals, alkaline earth metals or ammonia and amines
and the herbicidal compounds (b) or their environmentally
compatible salts of, for example, alkali metals, alkaline earth
metals or ammonia and amines are capable of effecting very good
control of broadleaved weeds and grass weeds in the crop rice
without damaging the crop plants, an effect which is observed even
when low rates of application are used.
[0279] Taking into consideration the versatility of the application
methods, the herbicidal mixtures and herbicidal compositions
according to the invention can also be employed in a further number
of crop plants for eliminating undesirable plants. Suitable crops
are, for example, the following:
[0280] Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus
officinalis, Beta vulgaris ssp. altissima, Beta vulgaris ssp. rapa,
Brassica napus var. napus, Brassica napus var. napobrassica,
Brassica rapa var. silvestris, Camellia sinensis, Carthamus
tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis,
Coffea arabica (Coffea canephora, Coffea liberica), Cucumis
sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis,
Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium
arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus
annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus,
Ipomoea batatas, Juglans regia, Lens culinaris, Linum
usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot
esculenta, Medicago sativa, Musa spp., Nicotiana tabacum
(N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus,
Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus
avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus
communis, Saccharum officinarum, Secale cereale, Solanum tuberosum,
Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense,
Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea
mays,
[0281] In addition, the herbicidal mixtures and herbicidal
compositions according to the invention can also be used in crops
which tolerate the action of herbicides due to breeding, including
genetic engineering methods.
[0282] The herbicidal mixtures and herbicidal compositions
according to the invention may be applied pre- or post-emergence.
If the active ingredients are less well tolerated by certain crop
plants, application techniques may be used in which the herbicidal
compositions are sprayed, with the aid of the spraying equipment,
in such a way that the active ingredients reach the leaves of the
sensitive crop plants as little as possible while reaching the
leaves of undesirable plants which grow underneath, or the bare
soil surface (post-directed, lay-by).
[0283] The compositions according to the invention can be applied,
for example in the form of ready-to-spray aqueous solutions,
powders, suspensions, also highly-concentrated aqueous, oily or
other suspensions or dispersions, emulsions, oil dispersions,
pastes, dusts, materials for spreading or granules, by means of
spraying, atomizing, dusting, spreading or pouring. The use forms
depend on the intended purposes; in any case, they should guarantee
the finest possible distribution of the active ingredients
according to the invention.
[0284] Suitable inert additives are mineral oil fractions of medium
to high boiling point, such as kerosene or diesel oil, furthermore
coal tar oils and oils of vegetable or animal origin, aliphatic,
cyclic and aromatic hydrocarbons, eg. paraffin,
tetrahydronaphthalene, alkylated naphthalenes or their derivatives,
alkylated benzenes or their derivatives, methanol, ethanol,
propanol, butanol, cyclohexanol, cyclohexanone or strongly polar
solvents such as N-methylpyrrolidone or water.
[0285] Aqueous use forms can be prepared from emulsion
concentrates, suspensions, pastes, wettable powders or
water-dispersible granules by adding water. To prepare emulsions,
pastes or oil dispersions, the substances, as such or dissolved in
an oil or solvent, can be homogenized in water by means of wetting
agent, adhesive, dispersant or emulsifier. Alternatively, it is
possible to prepare concentrates composed of active ingredient,
wetting agent, adhesive, dispersant or emulsifier and, if desired,
solvent or oil, which are suitable for dilution with water.
[0286] Suitable surfactants are the alkali, alkaline earth and
ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-,
naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty
acids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and
fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and
octadecanols, and of fatty alcohol glycol ethers, condensates of
sulfonated naphthalene and its derivatives with formaldehyde,
condensates of naphthalene or of the naphthalenesulfonic acids with
phenol and formaldehyde, polyoxyethylene octylphenol ether,
ethoxylated isooctylphenol, octylphenol or nonylphenol, alkylphenyl
polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl
polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene
oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl
ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol
ether acetate, sorbitol esters, lignosulfite waste liquors or
methylcellulose.
[0287] Powders, materials for spreading, and dusts, can be prepared
by mixing or concomitantly grinding the herbicidal mixture with a
solid carrier.
[0288] Granules, eg. coated granules, impregnated granules and
homogeneous granules, can be prepared by binding the active
ingredient onto solid carriers. Solid carriers are mineral earths
such as silicas, silica gels, silicates, talc, kaolin, limestone,
lime, chalk, bole, loess, clay, dolomite, diatomaceous earth,
calcium sulfate, magnesium sulfate, magnesium oxide, ground
synthetic materials, fertilizers such as ammonium sulfate, ammonium
phosphate, ammonium nitrate, ureas, and products of vegetable
origin such as cereal meal, tree bark meal, wood meal and nutshell
meal, cellulose powders, or other solid carriers.
[0289] In general, the formulations comprise 0.01 to 95% by weight,
preferably 0.5 to 90% by weight, of the herbicidal mixture.
[0290] It may furthermore be advantageous to apply the herbicidal
mixtures and herbicidal compositions according to the invention
together in the form of a mixture with other crop protection
agents, for example with agents for controlling pests or
phytopathogenic fungi or bacteria. Also of interest is the
miscibility with mineral salt solutions, which are employed for
treating nutritional and trace element deficiencies. Non-phytotoxic
oils and oil concentrates may also be added.
[0291] The rates of application of pure herbicidal mixture, ie.
without formulation auxiliaries, are from 0.01 to 5 kg/ha,
preferably 0.03 to 4 kg/ha, especially preferably 0.1 to 3.0 kg/ha,
of active ingredient (a.i.), depending on the intended purpose, the
season, the target plants and the growth stage.
[0292] The herbicidal compositions according to the invention are
applied to the plants mainly by means of foliar sprays. They may be
applied by customary spraying techniques using amounts of
approximately 100 to 1000 l of spray mixture per ha, for example
using water as the carrier. An application of the compositions in
the so-called "low-volume" and "ultra-low-volume" method is also
possible, as is their application in the form of so-called
granules.
USE EXAMPLES
[0293] The herbicide mixtures were applied post-emergence (foliar
treatment), the sulfonylurea derivatives being applied in the form
of 10 to 75 percent granules and the herbicidal compounds (b) in
the formulation in which they exist as the commercial product.
[0294] The tests involved field trials with small plots at a sandy
loam site (pH 6.2 to 7.0) or sandy clay (pH 5.0 to 6.7) site.
[0295] The weeds were present in different sizes and development
stages, their height being, on average, 5 to 20 cm, depending on
the plant habit.
[0296] The herbicidal compositions were applied alone and also
jointly, in the latter case sometimes as a tank mix, sometimes as a
ready-mix. This was done using water (350 l/ha) as the distribution
vehicle, depending on the formulation of the active ingredients in
the form of emulsions, aqueous solutions or suspensions.
Application was effected with the aid of a mobile plot sprayer.
[0297] The test period extended over 3 to 8 weeks, and the stands
were also observed at later dates.
[0298] The damage caused by the herbicidal compositions was
assessed using a scale from 0% to 100% in comparison with untreated
control plots. Thus, 0 means no damage, and 100 means complete
destruction of the plants.
[0299] The examples which follow show the activity of the
herbicidal compositions which can be used according to the
invention without excluding the possibility of other uses.
[0300] In these examples, the method of S. R. Colby (1967):
Calculating synergistic and antagonistic responses of herbicide
combinations, Weeds 15, 20 et seq. was used to determine the value
E which can be expected when an action of the individual active
ingredients is merely additive.
[0301] The calculation was carried out using the formula 1 E = X +
Y - XY 100
[0302] where
[0303] X=percentage activity using preparation A at a rate of
application a
[0304] Y=percentage activity using preparation B at a rate of
application b
[0305] E=expected activity (in %) caused by A+B at rate of
application of a+b.
[0306] If the observed value exceeds the value E calculated using
Colby's formula, a synergistic effect is present.
[0307] The herbicidal compositions according to the invention have
a herbicidal activity which is higher than what can be expected
when applying Colby's formula compared with the observed activities
of the individual components . . . used alone.
* * * * *